Coloration of materials comprising cellulose derivatives



v lose or made with or containing cellulose ethers.

l5 factory process 'for imparting. substantially inrst' arediul z, 1938" I I 2,123,740

COLORATION OF MATERIALS COMPRISING CELLULOSE DERIVATIVES Arthur E. Murphy, Penna Grove, and Donovan E. Kvalnes, Carneys Point, N. J assignors to E. I. du Pont de Nemours &' Company, Wilmington, Del., a corporation of Delaware No Drawing. Application March 29, 1935,

Serial N0. 13,791

12 Claims. (0]. 85)

This invention relates to the dyeing, printing, by a consideration of the following illustrative or stencilling of artificial threads, yarns, fabrics, examples in which the quantities are stated in films or other products made with or containing parts by weight: cellulose acetate or other organic esters of cellu- Example 1 This invention relates more particularly to the 9 P Of the combination: D- 0-an 11ne dispersion of relatively water insoluble'coloring I Xylldine having t w ng formula:

matter or dyes. CH! v It is an object of this invention to produce superior-dispersions of substantially insoluble 0 O 10 coloring matters and organic compounds. A furtherobject is to devise a process whereby cellulose E derivatives may be colored readily and efliciently.

v A still yfurther object is to produce a more Satis is dispersed (apparently dissolved) by stirring in 100 parts of a 10% water solution of cetyl tri- 15 soluble coloring materials and organic compounds methyl ammonium bromide heated to the boiling to textile materials containing cellulose deriva- P Boiling water thenadded to make tives, and in particular containing cellulose hquor to a total of 30900 parts- T dyebath 1S ethers or esters. A still further object is to proraised to 4o'5oo and 100 parts ofrcenulose 2o vide an improved process for producing an tate silk yamin hank form are entered, the

aqueous dispersion of substantially insoluble mg temperature beingraised to 65-75 C. during dyes to be used m the dyeingof cellulose acetate half an hour and ma ntained at that temperatextile materia1s ture for one hour. The goods dyed an orange I These objects are attained according to the shade are lifted, rinsed and dried or otherwise herein described invention wherein cellulose definished desired- 25 rivatives are colored by treating. with a dispe'r- Example 2 sion of a substantially insoluble coloring material-or organic compound and a compound which t 33;. z g fi p wT upon dissociation gives a positively charged sur- 0 me avmg e o m ormula' 39 face active ion. In a more restricted sense it per- CH:

tains to the coloring oftextile materials containing a cellulose derivative by immersion inan :NN=N NH: aqueous dispersion of a substantially insoluble dye a d a compound which upon dissociation is pasted with one part of hexadecylbetaine and .35 gives a positively charged surface active'ion, in one part of .water. The paste is diluted with 200 as particular a quaternary ammonium, quaternary parts of boiling water and added, through a sieve phosphonium,;or tertiary sulfonium compound if necessary, to 2500 parts of cold water. 100 containing at least 10 carbon atoms. In its preparts of cellulose acetate silk are entered at about ferred embodiment this invention pertains to the 60 C. and the temperature slowly raised to 75 .40 'coloring of cellulose acetate textiles by immersing C. and the dyeing being continued until the req- 40 saidtextiles in an aqueous dispersion of a subllislte Shade of Orange is Obtained- The goods 'stantially insoluble dye and a quaternary amare then rinsed and dried.

monium derivative having the following general Example 3 formula: v

5 parts of the combination: p-mtro-aniline 45 xf aniline having the' following formula:

- om-Om-mQ-rrm wherein R1 represents a hydrocarbon radical of at least 6 carbon atoms, R2, R3 and R4 represent are ground with 1 p Of cetyl r methyl am- 50 hydrocarbon radicals which may be externally m r i This m x re is pastedwith 1. joined to form a heterocyclic ring, and X reprepart of water and then 3000 parts of water are sents an anion usually possessing practically added. The dyeing of the cellulose acetate (100 negligible surface active properties. parts) is carried out in the usual manner. An

.55 The invention may be more readily understood orange shade is obtained.

I Example 4 One part of .a 50% paste of the combination: 4- nitro-2'-methoxy'-4-(dimethylamino) azo benzene is pasted with one part of cetyl pyridinium bromide. 3000 parts of warm water are added and the dye bath heated to 60 C. 200 'parts of cellulose acetate silk are dyed a red shade.

' Example 5 2 parts of the combination: p-nitro-aniline cresidine having the following formula:

OCHa' is ground with 1 part of N-stenyl betaine.

mixture is pasted with 1 part of water and then diluted with 3000 parts water.

. customary manner to obtain a scarlet shade.

Example 6 One part of 1,4-diamino anthraquinone is milled with 1 part of cetyl trimethyl ammonium bromide. This mixture is pasted with 5 parts of water and then 3000 parts of water are added. 300 parts of cellulose acetate are dyed a violet shade.

Example 7 One part of .1,4,5,8-tetra amino anthraquinone is treated in the same manner as Example 6. 300 parts of cellulose acetate are dyed a blue shade.

Exdmple 8 2 parts of amino azo toluene are milled with 1 part of cetyl trlmethyl ammonium bromide and 14 partsv of dextrin. This mixture is pasted with 10 parts of water and then diluted to 6.000 parts with water. 200 parts of cellulose acetate are dyed a bright yellow shade.

Example 9 proportions of the various agents and the conditions of treatment may be varied within wide limits without departing from the scope hereof.

In place of cellulose acetate silk other fibers composed of cellulose derivatives may be selected. 4

For example, cellulose esters and ethers and cellulose derivatives generally. such-as cellulose propionate, cellulose butyrate, benzyl cellulose, amino cellulose and the numerous cellulose derivatives heretofore used in place of or in combination with cellulose'acetate are contemplated. These cellulose derivatives may be in-the form of artificial threads, yarns, fabrics, films, and the like. They may be used alone, in conjunction with one another, and/or in combination with natural silk,

cotton, wool and the various materials with which T cellulose acetate and related substances are combined in the industrial arts.

This

When the bath I is raised to 60 C. 200 parts of cellulose acetate silk in hank form are'entered-and dyed in the Organic compounds or coloring materials which are contemplated herein' are understood to include those organic compounds and coloring materials which have been used or are capable of use in the treatmentof the aforementioned cellulose derivatives or products containing such cellulose derivatives. These "materials are ordinarily either dyes or dye intermediates. They are insoluble or practically insoluble in water, and are referred to in the present description and claims as substantially insoluble. In their practical application they may be used for dyeing, printing or stencilingof the materials'comprised herein. In general, dyes or dye intermediates for the coloring of cellulose acetate silk are preferred... A few' representative classes of materials from this group are: substantially insoluble azo dyes, such as diazotized nitro amines coupled with amines, N dialkylamines, N alkyl (hydroxy alkyl) amines, N-di-(hydroxy-alkyl)-amines and the reduction products of such combinations; basic derivatives of the anthraquinone series, such as amino anthraquinones, aminohydroxy anthra-' quinones, or their derivatives such as l-hydrox'y- 4-para-tolylamino-anthraquinone, and the .like;

-nitro-diphenylamine derivatives; simple amino bases for use in the production of azo dyes such as dianisidine, etc. It is, of course, to be understood'that the aforementioned dyes and intermediates are illustrative merely of the compounds which are to be used in the treatment of cellulose derivatives as deflned herein. Other compounds related thereto or widely differing therefrom but which are capable of use in this connection are also contemplated.

The aforementioned dyes, intermediates and related materials may be dispersed by mixing them in finely divided form with the dispersing agent or agents described herein. Mixing may be accomplished in the dry phase or before drying. The mixture may be heated under atmospheric pressure or under either superatmospheric or subatmospheric pressure, in the presence or absence of water. Where the coloring agents are .azo dyes, they may be coupled in the presence of a dispersing agent or mixture thereof and the resulting mixture subsequently dried. Moreover, the dye may be dissolved in a solvent and the resulting solution poured into an aqueous solution of the dispersing agent or mixture thereof. This aqueous solution may or may not contain protective colloids. The substantially insoluble dye may be treated with-a combination of the dispersing agent and an auxiliary solvent. The dispersed modification of the coloring material may be utilized for the dyeing of cellulose derivatives generally and cellulose acetate in particular by simply treating such dispersed modification with hot or cold water, filtering or pouring into the dye bath, which bath may be acid, neutral or alkaline, and conducting the dyeing in the customary manner.

Dispersing agents contemplated herein are those compounds which upon dissociation give a positively charged surface active ion. Compounds which are particularly adapted for this purpose are quaternary ammonium, quaternary phosphonium, and tertiary sulfonium compounds containing a positively charged surface active ion.

Those compounds are preferable which contain at least 10 carbon atoms. Where the aforementioned or related compounds contain a hydrocarbon chain of at least 6 carbon atoms, and

preferably from 12 to 18 carbon atoms, they have been found to be quite satisfactory. In the case Ri- N R; 1%

wherein R1 represents a hydrocarbon radical of at least 6 carbon atoms, R2, R3 and R4 represent hydrocarbon radicals which may be externally joined to form a heterocyclic ring, and X represents an anion possessing practically negligible surface active properties. In the above formula X is preferably chlorine or bromine; R1 is preferably an aliphatic hydrocarbon radical containing at least 6 carbon atoms and in particular a straight chain aliphatic hydrocarbon radical containing from 12 to 18 carbon atoms; R2, R3 and R4 are preferably hydrocarbon radicals of open chain or cyclic derivation, for example, R2, Ra and R4 may represent methyl or ethyl groups or their higher homologues, or they may be externally joined to form a heterocyclic ring in which the nitrogen nucleus is a hetero atom. The aforementioned heterocyclic ring may represent pyridine, quinoline, isoquinoline, partially or completely reduced quinoline, piperidine, morpholine, and the like. Where R1, R2, R3 or Racontains a salt forming group such as the carboxylic acid or sulfonic acid group it is contemplated that inner salts analogous to the betaine type may be produced therefrom, for instance by treatment with analkali. Compoundsof the betaine type are described in considerable detail in a copending application, Serial No. 13,664, filed by Downing and Johnson of even date herewith. The instructlons of said application when modified in accordance with the present invention are to be considered as a part hereof in the same manner as if they were incorporated herein.

ammonium compounds or in addition thereto quaternary phosphonium compounds may be used.

A few of the many compounds which are contemplated for use herein as dispersing agents will now be given. These compounds are principally quaternary ammonium compounds and tertiary sulfonium compounds. However, attention is called to the fact that several of the compounds Lcontainhydrogen in place of the alkyl groups of a quaternary ammonium compound.

Cetyl trimethyl'ammonium bromide Octadecyl. trimethyl ammonium chloride Distearyl ,dimethyl ammonium bromide Cetyl pyridinium bromide Hexadecyl betaine (from alpha halogenated stearic acid+trimethylamine) N-stearyl alpha betaine (from stearyl dimethylamine+chloracetic acid) N -dimethyI stearyl alanine Octadecyl cyclohexyl dimethyl ammonium bromide Condensation product of 2 moles of stearyl dimethyl-amine-i-l mole of 1,3-dichloro propanol-2 N-lauryl alpha betaine N-stearyl methyl alpha betaine N-stearyl beta betaine sulfate (inner salt of N-stearyl choline sulfate) -N' -lauryl beta betaine sulfate (inner salt of N-lauryl choline sulfate) N-stearyl beta betaine N-stearyl beta hydroxy gamma betaine sulfonate N-stearyl beta hydroxygamma betaine sulfate g Cetyl trimetbyl ammonium chloride Beta diethyl amino ethyl oleyl amide acetate Beta diethyl amino ethyl oleyl amide hydrochloride 1 I Trimethyl ammonium methyl sulfate of amino oleyl ethylene diamine Trimethyl 'eicosyl ammonium iodide Octadecyl pyridinium bromide Trimethyl dodecyl ammonium bromide Trimethyl dodecyl ammonium iodide Octadecyl beta hydroxyethyl morpholinium bromide Cetyl beta hydroxyethyl morpholinium bromide Triethyl octadecyl ammonium bromide Triethyl cetyl ammonium bromide Stearamido phenyl trimethyl. ammoniu methyl sulfate Octadecyl pyridinium chloride I Octadecyl pyridinium iodide Octadecyl alpha picolinium bromide Octadecyl quinolinium bromide Dodecyl pyridinium bromide 'Heptadecylamine hydrochloride Hexadecylamine hydrochloride Dodecylamine hydrochloride Octadecyl diethyl amine hydrochloride Methyl butyl hexadecyl sulfonium chloride Methyl butyl hexadecyl sulfonium methyl sulfate Methyl benzyl hexadecyl sulfonium chloride Methyl cyclohexyl hexadecyl sulfonium chloride 'Benzothiazole 2 cetyl methyl sulfonium methyl sulfate 4-Methyl benzothiazole-Z-cetyl methyl sulfonium methyl sulfate Para cetyl phenyl dimethyl sulfonium methyl sulfate Hexadecyl trimethyl phosphonium chloride The aforementioned dispersing agents may beused either alone or in admixture with one another. They may also be used in admixture with prior art wetting, detergent, emulsifying and dispersing agents or assistants therefor. connection it may be stated that since the dispersing agents referred to herein are capable of dissociating into positively charged surface active ions it is in general advisable to mix therewith only compounds which are likewise capable of dissociating with the production of positively charged surface active ions.

As many apparently widely different embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that the invention is not limited tothe specific embodiments thereof except as defined in the appended claims.

We claim: H 1. A process for coloring materials comprising organic substitution derivatives of cellulose which comprises applying thereto a substantially insoluble coloring compound capable of coloring cellulose acetate in the form of an aqueous dishaving at least six carbon atoms.

In this 2. A process for coloring materials comprising cellulose acetate whclch comprises applying thereto a substantially insoluble coloring compound capable of coloring cellulose acetate in the form of an aqueous dispersion obtained with the aid of a surface active compound selected from the group consisting of ammonium, sulfonium, and phosphonium compounds which contain a positively charged ion that contains an aliphatic hydrocarbon group having at least six carbon atoms.

3. A composition of matter applicable for the dyeing of cellulose acetate comprising a substantially insoluble coloring compound capable of coloring cellulose acetate and a surface active compound selected from the group consisting of ammonium, sulfonium, and phosphonium compoundswhich contain a positively charged .ion that contains an aliphatic hydrocarbon group having'at least six carbon atoms, said surface active compound being present in such a proportion that said composition of matter can be dispersed in water.

4. A process for the dyeing of materials comprising cellulose acetate which comprises treating said materials with an aqueous dispersion of a substantially insoluble dye capable of coloring cellulose acetate, said dispersion having been obtained with the aid of a surface active compound selected from the group consisting of ammonium, sulfonium, and phosphonium'compounds which contain a positively charged ion that contains an aliphatic hydrocarbon group having from twelve to eighteen carbon atoms.

5. A composition of matter applicable for the dyeing of cellulose acetate comprising a substantially insoluble dye capable of coloring cellulose acetate and a surface active compound selected 'i'rom the group consisting of ammonium, sulfonium, and phosphonium compounds which contain a positively charged ion that contains an allphatic hydrocarbon group having from twelve to eighteen carbon atoms, said surface active compoundv being present in such a proportion that said composition ofmatter can be dispersed in water.

6. A process for the dyeing of textile materials comprising cellulose acetate which comprises applying thereto an aqueous dispersion of a relatively water-insoluble organic compound capable of coloring cellulose acetate wherein the dis-' persing agent is solely a quarternary ammonium compound, the positive ion of which contains a straight chain aliphatic hydrocarbon group having from twelve to eighteen carbon atoms.

'7. A dyeing preparation containing no protective colloid comprising arelatively water-insoluble organic compound'capable of coloring cello-i lose acetate and a quaternary ammoniumcom-g.

pound, the positive ion of which contains a straight chain alkyl group having from twelve to eighteen carbon atoms, said quartemary ammonium compound being present in such a proportionthat said dyeing preparation is dispersible in water.

8. A process of dyeing textile materials comprising cellulose acetate which comprises applying thereto arelatively water insoluble organic compound capable of coloring cellulose acetate in the form of an aqueous dispersion prepared by using a tetra-alkyl ammonium halide containing one alkyl group having from twelve to eighteen carbon atoms in a straight chain as the dispersing agent.

9. A dyeing preparation which is dispersible in water comprising a relatively water-insoluble organic compound capable of coloring cellulose acetate and a tetra-alkyl ammonium halide in which one of the alkyl groups contains from twelve to eighteen carbon atoms in a straight chain.

10. A process of dyeing textile materials comprising cellulose acetate which comprises applying thereto an aqueous dispersion of a substantially water-insoluble organic compound capable of coloringcelluiose acetate, said dispersion having been prepared by using as a dispersing agent an alkyl pyridinium halide wherein the alkyl group contains a straight chain having from twelve to eighteen carbon atoms.

11. A process for the coloration of textile materials comprising cellulose acetate which comprises applying thereto a relatively insoluble coloring in the form of an aqueous dispersion obtained with the aid of a betaine which contains as one of its substituents an alkyl igroup having a straight chain containing from twelve to eighteen carbon atoms.

12. A dyeing preparation which is dispersible in water and useful in connection with the dyeing of cellulose acetate comprising asubstantially water-insoluble organic compound capable of coloring cellulose acetate and a betaine which contains as one of its substituents an alkyl group having a straight chain containing from twelve to eighteen carbon atoms.

ARTHUR R. MURPHY. DONOVAN E. KVALNES.

compound capable of coloring" cellulose acetate 

